CN1902133A - Method for treating metal-containing solutions - Google Patents
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- CN1902133A CN1902133A CNA200480039132XA CN200480039132A CN1902133A CN 1902133 A CN1902133 A CN 1902133A CN A200480039132X A CNA200480039132X A CN A200480039132XA CN 200480039132 A CN200480039132 A CN 200480039132A CN 1902133 A CN1902133 A CN 1902133A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/325—Emulsions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
- C02F2209/008—Processes using a programmable logic controller [PLC] comprising telecommunication features, e.g. modems or antennas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/911—Cumulative poison
- Y10S210/912—Heavy metal
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Abstract
A method for treating an electroless plating liquid or other metal-containing solution that also contains reducing agents. The method includes providing a reaction vessel containing an anode, a cathode, and a hydrogen ion-permeable membrane separating the anode and the cathode, placing the metal-containing liquid in contact with the anode, placing a catholyte solution in contact with the cathode; driving an electrical current through the anode and the cathode to oxidize the reducing agents present, and removing the used catholyte solution and the partially treated liquid from the electrodes, optionally from the reaction vessel to separate reservoirs. The partially treated liquid and an anolyte solution are placed in contact with the cathode and anode, respectively, and a current is again driven through the anode and cathode, plating a majority of the metal ions onto the cathode. The steps of oxidizing the reducing agents and plating the metal ions may also be reversed in order.
Description
Technical Field
The present invention relates to a method and apparatus for treating a metal-containing solution by electrolysis. The method and apparatus provide for the removal of metals from a solution, rendering the solution environmentally acceptable for disposal, and the recovery of valuable metals from the solution.
Background
Electroless plating is a common method for introducing a metal coating on a target. To coat an object by electroless plating, a metal compound is placed in solution and the elemental metal is subsequently deposited by chemical reaction. A highly uniform metal coating such as nickel, copper, silver, gold, platinum or palladium can be formed on an object using electroless plating. Electroless plating is often used in the electronics industry, such as in the processing of semiconductor wafers.
Over time and with continued use, the electroless plating solution is consumed and/or contaminated with byproducts of the plating process, requiring replacement of the solution. However, in terms of environmental aspects, the waste plating solution contains metal compounds. Spent plating solutions also can volatilize large amounts of hydrogen gas, presenting explosion and combustion hazards. Therefore, various methods have been proposed to treat the waste plating solution.
Various methods of treating spent plating solutions are described in U.S. Pat. No.6,391,209, the contents of which are incorporated herein by reference. These methods include treating such solutions with an oxidizing agent such as hydrogen peroxide.
Another method involves chemical reduction of the metal followed by precipitation as an organometallic complex. The plating solution may also be treated by exposure to ozone, ultraviolet light, or hydrogen peroxide, or a combination thereof.
U.S. Pat. No.5,730,856, the contents of which are incorporated herein by reference, describes a method of treating an electroless plating solution by electrolytic oxidation with simultaneous vibration and fluidization by an oscillating stirrer.
Electrochemical cells are also used to remove metals from metal-containing solutions, such as electroless plating solutions. U.S. Pat. No.6,162,333(Lemon et al), the contents of which are incorporated herein by reference, describes such a cell.
Summary of The Invention
There is provided a method of treating a metal-containing solution, wherein the metal-containing solution further comprises a reducing agent, the method comprising the steps of:
providing a reaction vessel comprising an anode, a cathode, and a hydrogen ion permeable membrane separating the anode and the cathode;
contacting a metal-containing liquid to be treated in a reaction vessel with an anode;
contacting a catholyte solution with a cathode;
placing an anode and a cathode in electrical communication with a power source for a first time, and driving an electrical current through the cathode and the anode until at least a majority of the reducing agents in the metal-containing liquid are oxidized to produce an intermediate liquid and a used catholyte solution;
removing the used catholyte solution from contact with the cathode and the intermediate liquid from contact with the anode, optionally from the reaction vessel separately, into first and second reservoirs;
contacting the intermediate liquid with a cathode;
contacting an anolyte solution with an anode;
the anode and cathode are placed in electrical communication with a power source for a second time and an electrical current is driven through the cathode and anode until a majority of the metal ions of the intermediate liquid plate onto the cathode to form a treated solution.
The order of the steps of the treatment process may also be altered such that the process comprises the steps of:
providing a reaction vessel comprising an anode, a cathode, and a hydrogen ion permeable membrane separating the anode and the cathode;
contacting a metal-containing liquid in a reaction vessel with a cathode;
contacting an anolyte solution in a reaction vessel with an anode;
placing an anode and a cathode in electrical communication with a power source, and driving an electrical current through the cathode and the anode until at least a majority of the metal ions in the metal-containing liquid are plated onto the cathode to produce an intermediate liquid;
removing the intermediate liquid from contact with the cathode and the anolyte solution from contact with the anode, optionally from the reaction vessel separately, into first and second reservoirs;
contacting the intermediate liquid with the anode;
contacting a catholyte solution with a cathode;
placing the anode and cathode in electrical communication with a power source a second time and driving an electricalcurrent through the cathode and anode until at least a majority of the reducing agents of the metal-containing liquid are oxidized to form a treated solution. A used catholyte solution is also formed.
In this method, the catholyte may be a solution of an iron salt, in one embodiment a solution of iron sulfate, and the anolyte may be a solution of sodium sulfate, in one embodiment. The catholyte and anolyte may have approximately equal ionic concentrations as the respective solutions processed in the reaction vessel.
Brief description of the drawings
FIG. 1 is a schematic view of an apparatus for treating an electroless plating liquid.
Detailed Description
One embodiment of an apparatus for treating a metal-containing liquid is described with reference to FIG. 1. The processing apparatus 10 comprises a reaction vessel 12. Inside the reaction vessel 12 are an anode 14 and a cathode 16. The anode may be any metal that does not oxidize during the process, such as stainless steel, and the cathode may be brass. The anode 14 and cathode 16 are in communication with a power source 15, which in some embodiments is a direct current power source. Also contained within the reaction vessel 12 is a hydrogen ion permeable membrane 18 which separates and provides two separate spaces within the reaction vessel 12 containing an anode 14 and a cathode 16, respectively.
An electroless plating solution or similar metal-containing solution is placed in reaction vessel 12 in contact with anode 14. A catholyte solution is placed in reaction vessel 12 in contact with cathode 16. The concentration of the catholyte solution is preferably about equal to the ionic concentration of the metal-containing liquid. The catholyte solution may be a solution of any non-electrochemically active salt. The non-electrochemically active salt may be an iron salt, such as iron sulfate. By "non-electrochemically active" is meant that neither the cationic nor anionic portions of the salt react under the process conditions, i.e., do not cause side reactions in the process. For example, a salt that generates chloride ions cannot be considered non-electrochemically active because the chloride ions are oxidized under the reaction conditions and form chlorine gas.
An anode 14 and a cathode 16 in communication with a power source 15 are driven by the current. In one embodiment, the current is applied at about 1 to about 10 amps, although other current levels may be used. Electrolysis proceeds until at least a majority of the reducing agents in the metal-containing solution are oxidized at anode 14. This oxidation prevents the reducing agent from generating hydrogen. At the same time, the ions in the catholyte solution are reduced. For ferric sulfate solutions, ferrous sulfate is formed.
Preferably, electrolysis is continued until substantially all of the reducing agent is oxidized. The progress of the reduction can be monitored by oxidation-reduction potential (ORP), colorimetry (if one of the species absorbs visible or ultraviolet light), or other known methods. The treatment may be continued for a sufficient time and at a sufficient current to oxidize all of the reducing agent stoichiometrically. For example, if the reducing agent concentration is 1 g/l, the molar amount of reducing agent is 58 g/mol, and a maximum of 6 electrons are given per molecule during reduction, then it takes 33 minutes to complete electrolysis with 5 amps of current applied (assuming 100% current efficiency):
1 g/mol (58 g/mol). times. (6 mol e)-Per mole X (96,500 coulombs/sec e)-) 33 minutes/5 coulomb/sec/60 sec/min.
The intermediate solution, i.e. the metal-containing solution at least the majority of which has been oxidized, is brought out of contact with the anode. In certain embodiments, it is removed from reaction vessel 12 and placed in first reservoir 20. At the same time, the used catholyte solution is removed from contact with the cathode. In some embodiments, it is placed in reservoir 21. The intermediate solution is then contacted with cathode 16 and, if necessary, returned to reaction vessel 12. The anolyte solution is then brought into contact with anode 14 within reaction vessel 12.
The anolyte solution preferably has the same ionic concentration as the intermediate solution. The anolyte solution is a non-electrochemically active salt solution which may be a sodium salt, such as sodium sulfate, but may also be a sulfate salt such as ferrous sulfate. The anode 14 and cathode 16 are placed in communication with a power source 15 and driven again by an electric current. Typically, in some embodiments, the applied current is about 1 to about 10 amps, although other current levels may be used. Electrolysis proceeds until at least a majority of the oxidizing agent (i.e., metal ions) in the intermediate solution is plated onto cathode 16 as the elemental metal. Hydrogen is produced from anode 14 due to the hydrolysis of water.
Preferably, substantially all of the metal ions are plated onto cathode 16. Progress of the reaction may be monitored by ORP, colorimetry, or other known methods, or, as noted above, the treatment may be continued at sufficient current for a sufficient time to oxidize all of the reducing agents according to stoichiometric calculations.
At the end of the second electrolysis step, the treated liquid in contact with the cathode, from which the metal compounds and reducing agent have been removed, is discharged toa container 25 for storage or disposal. The used anolyte may also be transferred to a separate reservoir 26 for storage or disposal. The reducing agent in the waste plating solution produced in this process has been oxidized and thus does not generate H in the future2Gas, and has removed plating metal ions from the spent plating solution. In addition, when the ferrous sulfate solution from the first electrolysis step is stored in the reservoir 21, ferric sulfate can be regenerated by bubbling air or oxygen through the ferrous sulfate solution.
The process may be carried out in the reverse order, i.e. first removing the oxidising agent and then oxidising the reducing agent. In this example, an electroless plating solution or similar metal-containing liquid is placed in reaction vessel 12 in contact with cathode 16. An anolyte solution is placed within reaction vessel 12 in contact with anode 14. The anolyte solution preferably has about the same ionic concentration as the metal-containing liquid. The anolyte solution may be any non-electrochemically active salt solution. For example, the anolyte may be a sodium salt, such as sodium sulfate, but may also be a sulfate salt such as ferrous sulfate. The anode 14 and cathode 16 are connected to a power source 15, which is preferably a direct current power source. Electrolysis is carried out until at least a majority of the oxidizing agent (i.e., metal ions) in the metal-containing liquid is plated onto cathode 16 as elemental metal. Hydrogen is produced from anode 14 due to the hydrolysis of water. Preferably, substantially all of the metal ions are plated onto the cathode. Progress of the reaction may be monitored by ORP, colorimetry, or other known methods, or, as noted above, the treatment may be continued at sufficient current for a sufficient time to oxidize all of the reducing agents according to stoichiometric calculations.
The intermediate solution, i.e. the metal-containing solution at least the majority of which has been oxidized, is then brought out of contact with the anode. In some embodiments, it is removed from reaction vessel 12 and placed in reservoir 21. At the same time, the used anolyte solution is removed from contact with the anode. In some embodiments, it is placed in reservoir 26. The intermediate solution is then brought into contact with the anode 14 and, if necessary, returned to the reaction vessel 12. The catholyte solution is then brought into contact with cathode 16 within reaction vessel 12. The cathode solution may be a solution of any non-electrochemically active salt. Suitable solutions include solutions of iron salts such as iron sulfate and sodium sulfate.
The catholyte solution preferably has about the same ionic concentration as the intermediate solution. The anode 14 and cathode 16 are in communication with a power source 15, again driven by an electrical current. As noted above, in some embodiments, the current is typically 1-10 amps, although other current levels may be used. Electrolysis proceeds until at least a majority of the reducing agents in the intermediate liquid are oxidized at anode 14. Preferably, substantially all of the reducing agent is oxidized. This oxidation prevents the reducing agent from generating hydrogen. At the same time, ions in the catholyte solution are reduced. For ferric sulfate, ferrous sulfate is formed. Progress of the reaction may be monitored by ORP, colorimetry, or other known methods, or, as noted above, the treatment may be continued at sufficient current for a sufficient time to oxidize all of the reducing agents according to stoichiometric calculations.
At the end of the second electrolysis step, the treated liquid in contact with the anode (from which the metal compounds and reducing agent have been removed) is discharged into a container 26 for storage or disposal. The used catholyte may also be transferred to a separate reservoir 25 for storage, recycling or disposal. When a ferrous sulfate solution is stored in reservoir 25, ferric sulfate may be regenerated by bubbling air or oxygen through the ferrous sulfate solution. The reducing agent in the waste plating solution produced in this process has been oxidized and thus does not generate H in the future2Gas, and has removed plating metal ions from the spent plating solution.
The reaction vessel 12 may also contain a sparger 28 in fluid communication with an inert gas source 30. The inert gas may be, for example, nitrogen or an inert gas such as helium or argon. The reaction vessel 12 may also contain a water removal valve 24 and a heat exchanger 29, such as a cooling jacket or coil through which cooling water is circulated. There may also be vents 32. The vent 32 is preferably in fluid communication with a hydrogen scrubber (not shown).
In treating the plating solution, the liquid is sparged with an inert gas such as nitrogen, helium or argon. Hydrogen gas released during the treatment of the plating solution is purged with the inert gas to form a sparge gas. Residual amounts of liquid entrained with the sparged gas are removed through the water trap 24. The at least partially dried sparge gas is then vented through vent 32, preferably to a hydrogen scrubber (not shown).
Heat is also generated during the process and can be removed by heat exchanger 29. The temperature of the plating solution is maintained at a temperature suitable for disposal or further processing. For example, the plating solution is maintained at a temperature of 50 ℃ or less during the treatment. The liquid may also be treated, for example, by contact with an ion exchange resin.
Examples
One embodiment of the process is further illustrated by the following example. This example does not constitute a limitation of the process in any way.
A used electroless plating solution containing cobalt ions as an oxidizing agent and dimethylamine borane (DMAB) as a reducing agent was treated in the following manner to prevent plating-out and spontaneous generation of hydrogen gas.
The first step is as follows: as described above, the used electroless plating solution is contacted with the anode (i.e., as an anolyte). The catholyte is an aqueous ferric sulfate solution. The oxidation reaction at the anode when current is applied is: DMAB → DMA + B (OH)3+6e-(ii) a The reduction reaction at the cathode is: . The anolyte and catholyte are then removed from the apparatus.
The second step is that: the used electroless plating solution (i.e., the solution in which DMAB has just been oxidized) from the above step is contacted with the cathode (i.e., as a catholyte). The anolyte is an aqueous solution containing sodium sulfate. The reduction reaction at the cathode when current is applied is: (ii) a The oxidation reaction at the anode is: 2H2O→4H++O2+4e-。
The result is that the used electroless plating solution has cobalt ions removed and DMAB oxidized so that the solution does not plate out and hydrogen gas is not spontaneously generated.
The methods and apparatus of the present invention are advantageous over prior systems because they allow for the rapid and cost-effective removal of metals and metal compounds from the plating solution with minimal hydrogen gas generation; the reducing agent is also oxidized at the anode and the oxidizing agent is reduced at the cathode, respectively, so that the reducing agent and the oxidizing agent are prevented fromreacting directly with each other in the bulk solution, which would proceed uncontrollably and generate hydrogen.
The entire process may be controlled by a programmable controller, and data recorded during the process may be fed to a computer which may be used to retrieve the remote data. The apparatus and method include a fully automatic microprocessor controller that can continuously monitor system operation, provide fault detection, pressure and/or temperature control and valve programming, and minimize operator involvement while ensuring reliability.
The device may include a system alarm that monitors for possible hazards, such as temperature or pressure excursions, to ensure system integrity. Alarm and warning conditions may be indicated on the operator interface and equipped with an alarm beeper.
It is to be understood that the embodiments described herein are by way of example only and that variations and modifications may be effected by one skilled in the art without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the present invention as described above. It should be understood that any of the above embodiments are only alternatives, but they may be combined.
Claims (18)
1. A method of treating a metal-containing liquid that also contains a reducing agent, the method comprising the steps of:
providing a reaction vessel comprising an anode, a cathode, and a hydrogen ion permeable membrane separating the anode and the cathode;
contacting a metal-containing liquid to be treated in a reaction vessel with an anode;
contacting a catholyte solution with a cathode;
placing an anode and a cathode in electrical communication with a power source for a first time, and driving an electrical current through the cathode and the anode until at least a majority of the reducing agents in the metal-containing liquid are oxidized to produce an intermediate liquid and a used catholyte solution;
removing the used catholyte solution from contact with the cathode and the intermediate liquid from contact with the anode, optionally each removed from the reaction vessel, to a first and second reservoir respectively;
contacting the intermediate liquid with a cathode;
contacting an anolyte solution with an anode;
the anode and cathode are placed in electrical communication with a power source for a second time and an electrical current is driven through the cathode and anode until a majority of the metal ions in the intermediate liquid plate onto the cathode to form a treated solution.
2. The method of claim 1, wherein the catholyte solution is a solution of a non-electrochemically active salt having an ionic concentration approximately equal to the ionic concentration of the metal-containing liquid.
3. The method of claim 2, wherein the catholyte solution is a ferric sulfate solution and the used catholyte solution is a ferrous sulfate solution.
4. The method of claim 3, further comprising the step of regenerating the ferric sulfate solution from the ferrous sulfate solution by bubbling a gas through the ferrous sulfate solution, the gas selected from the group consisting of air and oxygen.
5. The method of claim 3, wherein the anolytesolution is a solution of approximately equal ionic concentration as the intermediate liquid, the solution being selected from the group consisting of sodium salt solutions and sulfate salt solutions.
6. The method of claim 5, wherein the anolyte solution is selected from the group consisting of sodium sulfate and ferrous sulfate.
7. The method of claim 1, wherein the anolyte solution is a solution of approximately equal ionic concentration as the intermediate liquid, the solution being selected from the group consisting of sodium salt solutions and sulfate salt solutions.
8. The method of claim 7, wherein the anolyte solution is selected from the group consisting of sodium sulfate and ferrous sulfate.
9. The method of claim 1, wherein the current is applied from about 1 to about 10 amps for at least one of the first and second times while the anode and cathode are connected to the power source.
10. A method of treating a metal-containing liquid that also contains a reducing agent, the method comprising the steps of:
providing a reaction vessel comprising an anode, a cathode, and a hydrogen ion permeable membrane separating the anode and the cathode;
contacting a metal-containing liquid in a reaction vessel with a cathode;
contacting an anolyte solution in a reaction vessel with an anode;
placing an anode and a cathode in electrical communication with a power source and driving an electrical current through the cathode and the anode until at least a majority of the metal ions in the metal-containing liquid are plated onto the cathode to produce an intermediate liquid;
removing the intermediate liquid from contact with the cathode and the anolyte solution from contact with the anode, optionally from the reaction vessel separately to a first and second reservoir respectively;
contacting the intermediate liquid with the anode;
contacting a catholyte solution with a cathode;
placing the anode and cathode in electrical communication with a power source a second time and driving an electrical current through the cathode and anode until at least a majority of the reducing agents of the metal-containing liquid are oxidized to form a treated solution.
11. The method of claim 10, wherein the catholyte solution is a solution of an iron salt having an ionic concentration approximately equal to the ionic concentration of the intermediate liquid.
12. The method of claim 11, wherein the iron salt is ferric sulfate and the used catholyte solution is a ferrous sulfate solution.
13. The method of claim 12, further comprising the step of regenerating a ferric sulfate solution from the ferrous sulfate solution by bubbling a gas through the ferrous sulfate solution, the gas selected from the group consisting of air and oxygen.
14. The method of claim 12, wherein the anolyte solution is a solution of approximately equal ionic concentration as the intermediate liquid, the solution being selected from the group consisting of sodium salt solutions and sulfate salt solutions.
15. The method of claim 14, wherein the anolyte solution is selected from the group consisting of sodium sulfate and ferrous sulfate.
16. The method of claim 10, wherein the anolyte solution is a solution of approximately equal ionic concentration as the intermediate liquid, the solution being selected from the group consisting of sodium salt solutions and sulfate salt solutions.
17. The method of claim 16, wherein the anolyte solution is selected from the group consisting of sodium sulfate and ferrous sulfate.
18. The method of claim 8, wherein the current is applied from about 1 to about 10 amps for at least one of the first and second times while the anode and cathode are connected to the power source.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/749,946 | 2003-12-31 | ||
| US10/749,946 US6942810B2 (en) | 2003-12-31 | 2003-12-31 | Method for treating metal-containing solutions |
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| Publication Number | Publication Date |
|---|---|
| CN1902133A true CN1902133A (en) | 2007-01-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200480039132XA Pending CN1902133A (en) | 2003-12-31 | 2004-12-17 | Method for treating metal-containing solutions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6942810B2 (en) |
| EP (1) | EP1701920A4 (en) |
| JP (1) | JP2007521402A (en) |
| KR (1) | KR20060108735A (en) |
| CN (1) | CN1902133A (en) |
| IL (1) | IL176294A0 (en) |
| WO (1) | WO2005066078A1 (en) |
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| CN113620389B (en) * | 2020-06-24 | 2024-02-13 | 叶旖婷 | Method and device for treating wastewater by electric synergistic oxidation reaction |
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| JP2911393B2 (en) | 1995-07-25 | 1999-06-23 | 日本テクノ株式会社 | Method and apparatus for producing fertilizer aqueous solution from electroless nickel plating wastewater |
| US6245389B1 (en) | 1996-12-27 | 2001-06-12 | Nippon Chemical Industrial Co., Ltd. | Method for circulating electroless nickel plating solution |
| DE19719020A1 (en) * | 1997-05-07 | 1998-11-12 | Km Europa Metal Ag | Method and device for regenerating tinning solutions |
| JP2975577B2 (en) * | 1997-10-17 | 1999-11-10 | 国光鍍金工業株式会社 | Electrolytic treatment of electroless nickel plating wastewater |
| DE19829274C2 (en) * | 1998-07-01 | 2002-06-20 | Otb Oberflaechentechnik Berlin | Process for the recovery of precious metals |
| US6162333A (en) | 1999-01-22 | 2000-12-19 | Renovare International, Inc. | Electrochemical cell for removal of metals from solutions |
| US6391209B1 (en) | 1999-08-04 | 2002-05-21 | Mykrolis Corporation | Regeneration of plating baths |
| JP2001293485A (en) * | 2000-04-12 | 2001-10-23 | Kurita Water Ind Ltd | Method and device for treating hexavalent chromium- containing waste water |
| US6942779B2 (en) | 2000-05-25 | 2005-09-13 | Mykrolis Corporation | Method and system for regenerating of plating baths |
| JP2002219464A (en) * | 2001-01-30 | 2002-08-06 | Nec Corp | Electrolytic treatment method and system |
| US6878258B2 (en) | 2002-02-11 | 2005-04-12 | Applied Materials, Inc. | Apparatus and method for removing contaminants from semiconductor copper electroplating baths |
-
2003
- 2003-12-31 US US10/749,946 patent/US6942810B2/en not_active Expired - Fee Related
-
2004
- 2004-12-17 EP EP04814953A patent/EP1701920A4/en not_active Withdrawn
- 2004-12-17 KR KR1020067012975A patent/KR20060108735A/en not_active Application Discontinuation
- 2004-12-17 CN CNA200480039132XA patent/CN1902133A/en active Pending
- 2004-12-17 JP JP2006547236A patent/JP2007521402A/en active Pending
- 2004-12-17 WO PCT/US2004/042821 patent/WO2005066078A1/en not_active Application Discontinuation
-
2006
- 2006-06-14 IL IL176294A patent/IL176294A0/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112088223A (en) * | 2018-05-16 | 2020-12-15 | 罗伯特·博世有限公司 | Method for obtaining gold and/or silver and/or at least one platinum group metal from a component of a fuel cell stack or a component of an electrolysis cell |
| CN112456607A (en) * | 2020-10-28 | 2021-03-09 | 马鞍山市华茂机械科技有限公司 | Sewage treatment equipment for machining plant |
Also Published As
| Publication number | Publication date |
|---|---|
| IL176294A0 (en) | 2006-10-05 |
| EP1701920A1 (en) | 2006-09-20 |
| JP2007521402A (en) | 2007-08-02 |
| US20050139553A1 (en) | 2005-06-30 |
| US6942810B2 (en) | 2005-09-13 |
| EP1701920A4 (en) | 2010-09-01 |
| WO2005066078A1 (en) | 2005-07-21 |
| KR20060108735A (en) | 2006-10-18 |
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